Ester-containing amine-based liquid polyols and use in preparation of urethane compositions

ABSTRACT

ESTER-CONTAINING AMINE-BASED LIQUID POLYOLS ARE PREPARED BY THE REACTION OF ALKYLENE OXIDE CONDENSATES OF AMINES WITH HALOGEN-CONTAINING ORGANIC ACID ANHYDRIDES AND ALKYLENE OXIDES. THE POLYOLS ARE PARTICULARLY USEFUL IN THE PREPARATION OF FLAME-RETARDANT POLYURETHANE FOAMS.

United States Patent Oflice" 3,823,176 Patented July 9, 1974 3,823,176ESTER-CONTAINING AMlNE-BASED LIQUID POLYOLS AND USE IN PREPARATION OFURETHANE COMPOSITIONS William W. Levis, Jr., Wyandotte, and Louis C.Pizzini,

Trenton, Mich., assignors to BASF Wyandotte Corporation, Wyandotte,Mich.

No Drawing. Continuation-impart of application Ser. No. 728,814, May 13,1968, now Patent No. 3,585,185. This application May 7, 1971, Ser. No.141,408

'Int. Cl. C07c 101/00 US. Cl. 260-468 J 8 Claims ABSTRACT OF THEDISCLOSURE Ester-containing amine-based liquid polyols are prepared bythe reaction of alkylene oxide condensates of amines withhalogen-containing organic acid anhydrides and alkylene oxides. Thepolyols are particularly useful in the preparation of flame-retardantpolyurethane foams.

The present application is a continuation-in-part of US. Ser. No.728,814 filed May 13, 1968, now U.S. Pat. No. 3,585,185.

The invention relates to ester-containing amine-based liquid polyols andto the use thereof in the preparation of urethane compositions. Moreparticularly, the invention relates to ester-containing amine-basedliquid polyols having halogen atoms chemically bound therein and to theuse thereof in the preparation of flame-retardant polyurethane foams.

It has become increasingly important to impart flameresistant propertiesto polyurethane plastics. This is particularly true where cellularpolyurethanes are used, for example, as insulation, and to prevent therisk of fire in the daily use of other items. Numerous methods are knownfor imparting flame-resistant properties to polyurethane plastics. Forexample, in the production of the cellular polyurethanes one may usehalogenated compounds or derivatives of acids of phosphorus as theactive hydrogen-containing component and thus impart flame resistance.It is also possible to use compounds of antimony or boron. Moreover,non-reactive phosphorus or halogen-containing compounds may be used asadditives for this purpose. All of these substances are capable ofimparting some flame-resistant properties to polyurethane foam plastics.However, a disadvantage associated with these substances is that the useof increasing quantities leads to a serious impairment of the mechanicaland physical properties of the cellular polyurethanes. Moreover, as thequantity of the flame-resisting agents is increased, the problem ofmixing the components containing the flame-resisting agent with thebalance of the components leading to the production of a cellularpolyurethane plastic is increased.

It is an object of the present invention to provide novelester-containing amine-based liquid polyols which impart flame-resistantproperties to polyurethane compositions and which are substantiallydevoid of the foregoing disadvantages. It is a further object of thepresent invention to provide polyurethane compositions useful in thepreparation of foams, adhesives, binders, laminates, and coatings. Theseand other objects of the present invention will be apparent from thespecification and examples which follow.

The above objects are accomplished in accordance with the presentinvention by providing novel ester-containing amine-based liquid polyolshaving halogen atoms chemically bound therein and which are ofrelatively low viscosity. The novel ester-containing polyols of thepresent invention are prepared by the reaction of alkylene oxidecondensates of amines having at least two active hydrogen atoms with ahalogen-containing organic acid anhydride and an alkylene oxide.

As mentioned above, there are three essential reactants employed in thepreparation of the ester-containing polyols of the present invention,namely, an alkylene oxide condensate of an amine having at least twoactive hydrogen atoms, a halogen-containing organic acid anhydride, andan alkylene oxide. Alkylene oxides which may be employed in thepreparation of the ester-containing polyols of the present inventioninclude ethylene oxide, propylene oxide, the isomeric normal butyleneoxides, hexylene oxide, octylene oxide, dodecene oxide, methoxy andother alkoxy propylene oxides, styrene oxide, and cyclohexane oxide.Halogenated alkylene oxides may also be used, such as epichlorohydrin,epiiodohydrin, epibromohydrin, 3,3-dichloropropylene oxide,3-chloro-1,2- epoxypropane, 3-chloro-1,2-epoxybutane, 1-chloro-2,3

epoxybutane, 3,4-dichloro-1,2-epoxybutane, 1,4-dichloro-2,3-epoxybutane, 1-chloro-2,3-epoxybutane, and 3,3,3-trichloropropyleneoxide. Mixtures of any of the above alkylene oxides may also beemployed.

Alkylene oxide condensates of amines having at least two active hydrogenatoms which may be employed in the preparation of the ester-containingpolyols of the present invention are generally prepared by the catalyticcondensation of an alkylene oxide or mixture of alkylene oxides eithersimultaneously or sequentially with an amine having at least two activehydrogen atoms. Any of the alkylene oxides mentioned above may beemployed with propylene oxide and ethylene oxide being preferred.Representative amines include aliphatic amines having from one to twentycarbon atoms, such as methyl amine, ethyl amine, propyl amine, butylamine, octyl amine, decyl amine, dodecyl amine, cetyl amine, ethylenediamine, propylene diamine, butylene diamine, diethylene triamine,dipropylene triamine, and triethylene tetramine; aromatic amines havingfrom six to tweleve carbon atoms such as toluene diamine, aniline,methylene dianiline, naphthalene diamine, polymeric compositions ofmethylene dianiline and condensation products of formaldehyde andaniline, o-chloroaniline, and/or toluidine; heterocyclic amines such aspiperazine and trialkanolamines such as triethanol amine, triisopropanolamine, and tributanol amine. Generally, the condensates useful in thepresent invention will have a molecular weight between 100 and 10,000,preferably between 300 and 6,000.

In the preparation of the ester-containing amine polyols of the subjectinvention, it is also possible to employ a hydroxyl-containing compoundas a coinitiator with the above-described condensates. Any of the manyhydroxylcontaining compounds known in the art as evidenced by US. Pats.Nos. 1,922,459, 3,190,927, and 3,346,557 may be employed.Particularlypreferred coinitiators include those hydroxyl-containingcompounds prepared by the reaction of propylene oxide with acids ofphosphorus having a P 0 equivalency of from 72 to percent.

The third reactant employed in the preparation of the ester-containingpolyols is a halogen-containing organic acid anhydride. Typicalanhydrides are halogenated polycarboxylic acid anhydrides such asdichloromaleic anhydride, tetrabromophthalic anhydride,tetrachlorophthalic anhydride, 1,4,5,6,7,7-hexach1orobicyclo(2.2.l)-5-heptene-2,3 dicarboxylic anhydrides, hereinafter calledchlorendic anhydride, l,4,5,6,7,7hexachloro- 2-methylbicyclo(2.2.1-5-heptene-2,3-dicarboxylic anhydride, 1,4,5,6,7,7hexachlorobicyclo(2.2.1)-5-heptene-2- acetic-Z-carboxylic anhydride,5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-S,8-methano-2,3-naphthalene dicarboxylicanhydride, and 1,2,3,4,5,6,7,7-octachloro-3,6-methanol-1,2,3,6-tetrahydrophthalic anhydride. 'Mixtures of any of theabove anhydrides may also be employed as well as mixtures of the aboveanhydrides and non- 3 halogenated anhydrides such as phthalic anhydride,maleic anhydride, and trimellitic anhydride.

The ester-containing polyols of the present invention are generallyprepared by heating the three reactants at temperatures between 50 C.and 150 C., preferably between 75 C. to 150 C., for 0.5 to hours.Temperatures below 150 C. must be maintained to prevent the reaction ofcarboxy and hydroxy groups with the formation of water. The reaction isgenerally carried out under from zero to 100 p.s.i.g. Alternatively, thealkylene oxide condensates and the halogen-containing organic acidanhydride may be added to a reaction vessel and heated to 50 C. to 150C. for zero to ten hours. Thereafter, the alkylene oxide is added to thereaction mixture under pressure while maintaining the reactiontemperature of betweeen 75 C. and 150 C. After completion of thereaction, the reaction mixture may be filtered and is stripped ofvolatiles by heating for about one-half hour to three hours at 80 C. to110 C. under less than 10 mm. of mercury. If desired, a solvent inert tothe reaction may be employed in the preparation of the polyols of thepresent invention.

The amounts of reactants employed in the preparation of theester-containing polyols of the present invention may vary. Generally,however, a mole ratio of alkylene oxide condensate to anhydride of from1:0.1 to 1:6, preferably from 1:01 to 1:1, will be employed. The amountof alkylene oxide employed will be such to reduce the acid number of thealkylene oxide condensate-anhydride reaction mixture to five or less,preferably one or less. The hydroxyl number of the ester-containingpolyol will vary considerably. Generally, however, the polyols will havea hydroxyl number of from about to 600, preferably from about 35 to 400.

In a preferred embodiment of the present invention, the foregoingester-containing polyols are employed in the preparation of polyurethanecompositions, particularly polyurethane foams. The resultingpolyurethane products exhibit marked improvements in flame-retardantproperties without impairment of the other physical properties of theproducts. Moreover, the lower viscosity of these polyols enables them tobe useful in the preparation of sprayable polyurethane compositions. Thepolyurethane products are generally prepared by the reaction of theester-containing polyol with an organic polyisocyanate, optionally inthe presence of additional polyhydroxylcontaining components,chain-extending agents, catalysts, surface active agents, stabilizers,blowing agents, fillers,

and pigments. Suitable processes for the preparation of cellularpolyurethane plastics are disclosed in US. Reissue Pat. 24,514 togetherwith suitable machinery to be used in conjunction therewith. When wateris added as the blowing agent, corresponding quantities of excessisocyanate to react with the water and produce carbon dioxide may beused. It is also possible to proceed with the preparation of thepolyurethane plastics by a prepolymer technique wherein an excess oforganic polyisocyanate is reacted in a first step with the polyol of thepresent invention to prepare a prepolymer having free isocyanate groupswhich is then reacted in a second step with Water to prepare a foam.Alternately, the components may be reacted in a single working stepcommonly known as the one-shot technique of preparing polyurethanes.Furthermore, instead of water, low boiling hydrocarbons such as pentane,hexane, heptane, pentene, and heptene; azo compounds such asazohexahydrobenzodinitrile; halogenated hydrocarbons such asdichlorodifluoromethane, trichlorofluoromethane, dichlorodifiuoroethane,vinylidene chloride, and methylene chloride may be used as blowingagents.

Organic polyisocyanates which may be employed include "aromatic,aliphatic, and cycloaliphatic polyisocyanates and combinations thereof.Representative of these types are the diisocyanates such as m-phenylenediisocyanate, tolylene-2,4diisocyanate, tolylene-2,6-diisocyanate,mixtures of 2,4- and 2,6-, hexamethylene-l,6-

diisocyanate, tetramethylene-l,4-diisocyanate,cyclohexane-1,4-diisocyanate, hexahydrotolylene diisocyanate (andisomers), naphthylene-1,5-diisocyanate, l-methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4-diisocyanate, 4,4- biphenylenediisocyanate, 3,3-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl4,4 biphenyl diisocyanate, and 3,3'-dimethyldiphenylmethane 4,4diisocyanate; the triisocyanates such as 4,4,4"-triphenylmethanetriisocyanate, polymethylene polyphenylisocyanate and tolylene2,4,6-triisocyanate; and the tetraisocyanates such as 4,4-dimethyldiphenylmethane 2,2,5,5-tetraisocyanate. Especially useful dueto their availability and properties are tolylene diisocyanate,diphenylmethane-4,4'-diisocyanate and polymethylenepolyphenylisocyanate.

Crude polyisocyanate may also be used in the compositions of the presentinvention, such as crude toluene diisocyanate obtained by thephosgenation of a mixture of toluene diamines or crude diphenylmethaneisocyanate obtained by the phosgenation of crude diphenylmethyl diamine.The preferred unreacted or crude isocyanates are disclosed in U.S. Pat.No. 3,215,652.

As mentioned above, the ester-containing polyol may be employed as thesole polyhydroxyl-containing component or it may be employed along withthe polyhydroxyl-containing components commonly employed in the art.Representative of these components are hydroxylcontaining polyesters,polyalkylene polyether polyols, hydroxy-terminated polyurethanepolymers, polyhydric polythioethers, polyhydroxyl-containing phosphoruscompounds, polya'cetals, aliphatic polyols, aliphatic thiols includingalkane, alkene, and alkyne thiols having two or more -SH groups;diamines including both aromatic, aliphatic, and heterocyclic diamines,as well as mixtures thereof. Compounds which contain two or moredifferent groups within the above-defined classes may also be used suchas, for example, amino alcohols which contain an amino group and ahydroxyl group. Also compounds may be used which contain one -SH groupand one OH group as well as those which contain an amino group and a SHgroup.

Any suitable hydroxyl-containing polyester may be used such as areobtained, for example, from polycarboxylic acids and polyalcohols. Anysuitable polycarboxylic acid may be used such as oxalic acid, malonicacid, succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleicacid, fumaric acid, glutaconic acid, a-hydromuconic acid,fi-hydromuconic acid, OL-blltYl-Otethyl-glutaric acid,a-fl-diethylsuccinic acid, isophthalic acid, terephthalic acid,hemimellitic acid and 1,4-cyclohexane-dicarboxylic acid. Any suitablepolyhydric alcohol including both aliphatic and aromatic may be usedsuch as ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol,1,5-pentane diol, 1,4-pentane diol, 1,3-pentane diol, 1,6-hexane diol,1,7-heptane diol, glycerol, 1,l,1-tri methylolpropane,1,1,l-trimethylolethane, hexane-1,2,6- triol, u-methyl glucoside,pentaerythritol, and sorbitol. Also included within the term polyhydricalcohol are compounds derived from phenol such as2,2-(4,4'-hydroxyphenyl) propane, commonly known as Bisphenol A.

Any suitable polyalkylene polyether polyol may be used such as thepolymerization product of an alkylene oxide or of an alkylene oxide witha polyhydric alcohol. Any suitable polyhydric alcohol may be used suchas those disclosed above for use in the preparation of thehydroxylcontaining polyesters. Any suitable alkylene oxide may be usedsuch as ethylene oxide, propylene oxide, butylene oxide, amylene oxide,and heteric or block copolymers of these oxides. The polyalkylenepolyether polyols may be prepared from other starting materials such astetrahydrofuran and alkylene oxide-tetrahydrofuran copolymers;epihalohydrins such as epichlorohydrin; as well as am!- kylene oxidessuch as styrene oxide. The polyalkylene polyether polyols may haveeither primary or secondary hydroxyl groups and, preferably, arepolyethers prepared from alkylene oxides having from two to six carbonatoms such as polyethylene ether glycols, polypropylene ether glycols,and polybutylene ether glycols. The polyalkylene polyether polyols maybe prepared by any known process such as, for example, the processdisclosed by Wurtz in 1859 and Encyclopedia of Chemical Technology, Vol.7, pp. 257-262, published by Interscience Publishers, Inc. (1951) or inU.S. Pat. No. 1,922,459. Polyethers which are preferred include thealkylene oxide addition products of trimethylolpropane, glycerine,pentaerythritol, sucrose, sorbitol, propylene glycol, and 2,2-(4,4-hydroxyphenyDpropane and blends thereof having equivalent weights offrom 250 to 5,000.

Any suitable polyhydric polythioether may be used such as, for example,the condensation product of thiodiglycol or the reaction product of adihydric alcohol such as is disclosed above for the preparation of thehydroxyl-containing polyesters with any other suitable thioether glycol.

The hydroxyl-containing polyester may also be a polyester amide such asis obtained by including some amine or amino alcohol in the reactantsfor the preparation of the polyesters. Thus, polyester amides may beobtained by condensing an amino alcohol such as ethanolamine with thepolycarboxylic acids set forth above or they may be made using the samecomponents that make up the hydroxyl-containing polyester with only aportion of the components being a diamine such as ethylene diamine.

Polyhydroxyl-containing phosphorus compounds which may be used includethose compounds disclosed in our copending U.S. Patent Application Ser.No. 728,840, filed May 13, 1968, now U.S. Pat. No. 3,639,542. Preferredpolyhydroxyl-containing phosphorus compounds are prepared from alkyleneoxides and acids of phosphorus having a P equivalency of from about 72percent to about 95 percent.

Any suitable polyacetal may be used such as, for example, the reactionproduct of formaldehyde or other suitable aldehyde with a dihydricalcohol or an alkylene oxide such as those disclosed above.

Any suitable aliphatic thiol including alkane thiols containing at leasttwo --SH groups may be used such as 1,2-ethane dithiol, 1,2-propanedithiol, 1,3-propane dithiol, and 1,6-hexane dithiol; alkene thiols suchas 2-butene-1,4-dithiol; and alkyne thiols such as 3-hexyne-l,6-dithiol.

Any suitable polyamine may be used including aromatic polyamines such asp-amino aniline, 1,5-diamino naphthalene, and 2,4-diamino toluene;aliphatic polyamines such as ethylene diamine, 1,3-propylene diamine,1,4-butylene diamine, and 1,3-butylene diamine. Alkylene oxide adductsof any of the above polyamines may also be used, particularly propyleneoxide adducts of p-amino aniline and ethylene diamine.

Other compounds which do not necessarily fit within any of thepreviously set forth classes of compounds which are quite suitable inthe production of isocyanate-terminated prepolymers include thehydroxy-terminated polyurethane prepolymers such as a hydroxy-terminatedprepolymer made by reacting an isocyanate with several moles of analkylene glycol.

Chain-extending agents which may be employed in the preparation of thepolyurethane compositions of the present invention include thosecompounds having at least two functional groups bearing active hydrogenatoms such as water, hydrazine, primary and secondary diamines, aminoalcohols, amino acids, hydroxy acids, glycols, or mixtures thereof. Apreferred group of chain-extending agents includes water and primary andsecondary diamines which react more readily with the prepolymer thandoes water such as phenylene diamine 1,4-cyclohexane-bis- (methylamine),ethylene diamine, diethylene triamine, N- (2-hydroxypropyl)ethylenediamine, N,N-di(2-hydroxypropyl)ethyle'ne diamine, piperazine,Z-methylpiperazine, morpholine, anddodecahydro-1,4,19b-tetraazaphenalene.

Any suitable catalyst may be used including tertiary amines, such as,for example, triethylene diamine, N- methyl morpholine, N-ethylmorpholine, diethyl ethanolamine, N-coco morpholine,1-methyl-4-dimethylamino ethyl piperazine, 3-methoxy-N-dimethyl propylamine, N- dimethyl-N-methyl isopropyl propylene diamine,N,N-diethyl-3-diethyl amino propyl amine, dimethyl benzyl amine, and thelike. Other suitable catalysts are, for example, tin compounds such asstannous chloride, tin salts of carboxylic acids, such as dibutyltindi-Z-ethyl hexoate, tin alcoholates such as stannous octoate, as well asother organo metallic compounds such as are disclosed in U.S. Pat.2,846,408.

A wetting agent or surface active agent is generally necessary forproduction of high grade polyurethane foam according to the presentinvention, since in the absence of same the foams collapse or containvery large uneven cells. Numerous wetting agents have been foundsatisfactory. Nonionic surfactants and wetting agents are pr ferred. Ofthese, the nonionic surface active agents prepared by the sequentialaddition of propylene oxide and then ethylene oxide to propylene glycoland the solid or liquid organosilicones have been found particularlydesirable. Other surface active agents which are operative, although notpreferred, include polyethylene glycol ethers of long chain alcohols,tertiary amine or alkylolamine salts of long chain alkyl acid sulfateesters, alkyl sulfonic esters, and alkyl arylsulfonic acids.

Along with the ester-containing polyols of the present invention,non-reactive flame retardants may be employed in the preparation of thepolyurethane compositions of the present invention. Representative flameretardants include tris-2-chloroethylphosphate,tris-2,3-dibromopropylplfiosphate, antimony oxide, and polyammoniumphosp ate.

The following examples illustrate the nature of the invention. All partsare by weight unless otherwise stated.

EXAMPLE I A reaction vessel equipped with a thermometer, stirrer,nitrogen source, and heat exchange means was charged with 575 parts ofan amine polyol prepared by condensing propylene oxide with toluenediamine (hydroxyl number of 390) and 371 parts of chlorendic anhydride.The reaction vessel was then purged with nitrogen, vented to zerop.s.i.g., sealed, and while maintaining the temperature at 140 C., 87parts of propylene oxide was added to the reaction mixture over athree-hour period. The pressure at the end of the addition was between30-35 p.s.i.g. After completion of the oxide addition, the reactionmixture was stirred for three hours at 140 C. The reaction mixture wasthen stripped of volatiles by heating for two hours at 125 C. under apressure of less than 10 mm. of mercury. The resulting liquid producthad the following properties: hydroxyl number-2l7; acid number0.4; and19.8 percent chlorine.

A polyurethane foam was prepared from the abovedescribed liquidamine-based polyol employing the following ingredients: 50 parts of theester-containing aminebased polyol, 50 parts of an estercontainingpolyol prepared by the reaction of equimolar amounts of propylene oxide,tetrabromophthalic anhydride and a neutral phosphate polyol obtained bythe reaction of six moles of propylene oxide with one mole of percentphosphoric acid, 56 parts of tolylene diisocyanate, 1.5 parts of asilicone surfactant DC-193, 1.0 part of tetramethylene ethylene diamine,and 26 parts of trichlorofluoromethane. The foam was prepared byspraying the above ingredients in 10' x 10' boxes. The foam had adensity of 2.12 lbs./ft. and exhibited flame-retardant properties asevidenced by an 89 percent weight retention and a B flame heightdetermined in accordance with the Butler Chimney Test.

EXAMPLE II A reaction vessel equipped as described in Example I wascharged with 1492 parts of tetrachlorophthalic anhydride and 2250 partsof an amine polyol prepared by condensing propylene oxide with ethylenediamine (hydroxyl number of 460). The reaction vessel was then purgedwith nitrogen, vented to zero p.s.i.g., sealed, and heated to 125 C.Over a three-hour period, 455 parts of propylene oxide was added to thereaction mixture maintaining the temperature of the mixture at 125 C.The pressure at the end of the addition was between 20-25 p.s.i.g. Aftercompletion of the oxide addition, the reaction mixture was stirred fortwo hours at 125 C. The reaction mixture was stripped of volatiles byheating for one hour at 125 C. under a pressure of less than mm. ofmercury. The resulting liquid product had the following properties:hydroxyl number-221 and 14.1 percent chlorine.

A polyurethane foam was prepared employing 25 parts of theabove-described ester-containing polyol along with 55 parts of a polyolprepared by the reaction of propylene oxide with polymeric methylenedianiline, said polyol having a functionality of 2.3 and a hydroxylnumber of 337, and tolylene diisocyanate in an amount sufiicient toprovide an NCO/OH ratio of 1.28:1. Trichlorofluoromethane was employedas blowing agent. The resulting foam exhibited flame-retardantproperties.

EXAMPLE III A reaction vessel equipped as described in Example I wascharged with 776 parts of tetrabromophthalic anhydride, 4.78 parts ofsodium acetate, and 1956 parts of the amine polyol described in ExampleII. The reaction vessel was then purged with nitrogen, vented to zerop.s.i.g., and sealed. The reaction mixture was then heated to 140 C. andmaintained at this temperature for 0.5 hour. Over a two-hour period, 212parts of propylene oxide was added to the reaction mixture maintainingthe temperature of the mixture at 140 C, After completion of the oxideaddition, the reaction mixture was heated to 140 C. and stirred at thistemperature for three hours. The reaction mixture was then stripped ofvolatiles by heating for one hour at 110 C. under a pressure of lessthan mm. of mercury. The resulting liquid product had the followingproperties: hydroxyl number-292; acid number0.4; and 17.9 percentbromine.

A polyurethane foam was prepared employing parts of the above-describedester-containing amine-based polyol, 85 parts of a blend of polyolshaving a hydroxyl number of approximately 450, 1.0 part of diethylenetriamine, 1.0 part of dimethylamino ethanol, 1.0 part of siliconesurfactant DC-193, 41 parts of trichlorofiuoromethane, and 124 parts ofpolymethylene polyphenyl isocyanate. The foam exhibited the followingphysical properties:

Density, pcf. 1.79 Compressive strength, p.s.i.:

10% deflection 35.6 At yield point 35.9 Tensile strength, p.s.i 45.2Flame Test, D-l692-68:

(Sec.) 31 Distance consumed, in. 2.4

EXAMPLE IV A reaction vessel equipped as described in Example I wascharged with 776 parts of tetrabromophthalic anhydride, 4.78 parts ofanhydrous sodium acetate, and 1956 parts of an amine-based polyolprepared by reacting ethylene oxide with a condensate of propylene oxideand ethylene diamine, the polyol having a hydroxyl number of 450 and anethylene oxide content of 10 percent by weight. The reaction vessel wasthen purged with nitrogen, vented to zero p.s.i.g., and sealed. Thereaction mixture was then heated to 140 C. Over a three-hour period, 192parts of propylene oxide was added to the reaction mixture main tainingthe temperature of the mixture at 140 C. The pressure at the end of theaddition was between 90-95 p.s.i.g. After completion of the oxideaddition, the reaction mixture was heated for three hours at 140 C. andthen stripped of volatiles by heating for one hour at C. under apressure of less than 10 mm. of mercury. The liquid product had thefollowing properties: hydroxyl number-307; acid number0.5; and 18.0percent bro- Density, pcf. 1.78 Compressive strength, p.s.i.:

10% deflection 33.2 At yield point 33.7 Tensile strength, p.s.i 53.1Flame Test, D-1692-68:

(Sec.) 33 Distance consumed, in. 2.1

EXAMPLE V A reaction vessel equipped as described in Example I wascharged-with 143 parts of tetrachlorophthalic anhydride, 232 parts oftetrabromophthalic anhydride, 1.4 parts of anhydrous sodium acetate, and1566 parts of an amine-based polyol prepared by condensing propyleneoxide with polymeric methylene dianiline (hydroxyl number of 337 andfunctionality of 2.3). The reaction vessel was then purged withnitrogen, vented to zero p.s.i.g., and sealed. The reaction mixture wasthen heated to 140 C. Over a three-hour period, 116 parts of propyleneoxide was added to the reaction mixture maintaining the temperature ofthe mixture at 140 C. The pressure at the end of the addition wasbetween 40-45 p.s.i.g. After completion of the oxide addition, thereaction mixture was heated at 140 C. for three hours and was strippedof volatiles by heating for one hour at C. under a pressure of less than10 mm. of mercury. The product had the following properties: hydroxynumber 252; acid number0.3; 7.8 percent bromine, and 3.5 percentchlorine.

A polyurethane foam was prepared employing 100 parts of theabove-described ester-containing amine-based polyol, 1.5 parts ofsilicone surfactant DC-193, 1.0 part of tetramethyl ethylene diamine,66.5 parts of polymethylene polyphenylene isocyanate, and 30 parts oftrichlorofiuoromethane. The resulting foam had a density of 2.02 lbs/ft.and exhibited flame-retardant properties as measured by ASTM D-1692-68by being self-extinguishing in 23.7 seconds with 1.16 inches consumed.

EXAMPLE VI A reaction vessel equipped as described in Example I wascharged with 232 parts of tetrabromophthalic anhydride, 1.25 parts ofanhydrous sodium acetate, 124 parts of an amine-based polyol prepared bythe reaction of propylene oxide with toluene diamine (hydroxyl number of434) and 210.5 parts of a phosphorus polyol prepared by the reaction ofpropylene oxide with 100 percent phosphoric acid (hydroxyl number of400). The reaction vessel was then purged with nitrogen, vented to zerop.s.i.g., and sealed. The reaction mixture was then heated to 80 C. Overa three-hour period, 75.5 parts of propylene oxide was added to thereaction mixture maintaining the temperature of the mixture at 80 C.After completion of the oxide addition, the reaction mixture was heatedfor three hours and stripped of volatiles by heating for one hour at 80C. under a pressure of less than 10 mm. of mercury. The product had thefollowing properties: hydroxyl number-223; acid number0.2; and 24.6percent bromine.

What is claimed is:

1. An ester-containing amine-based liquid polyol prepared by thereaction at a temperature of from 50 C. to 150 C. for 0.5 hour to 10hours of (a) a condensate of an amine having at least two activehydrogen atoms selected from the group consisting of aliphatic amineshaving from one to twenty carbon atoms and aromatic amines having fromsix to twelve carbon atoms with an alkylene oxide selected from thegroup consisting of alkylene oxides having from 2 to 12 carbon atoms,halogenated alkylene oxides having from 2 to 4 carbon atoms and from 1to 3 halogen atoms and mixtures thereof,

(b) a halogen-containing organic acid anhydride selected from the groupconsisting of dichloromaleic anhydride, tetrabromophthalic anhydride,tetrachlorophthalic anhydride, l,4,5,'6,7,7hexachlorobicyclo(2.2.1)-5-heptene 2,3 dicarboxylic anhydride,hereinafter called chlorendic anhydride, l,4,5,6,7,7- hexachloro 2methylbicyclo(2.2.1)-5-heptene-2,3- dicarboxylic anhydride,1,4,5,6,7,7-hexachlorobicyclo (2.2.1)-5-heptene-Z-acetic-2-carboxylicanhydride, 5, 6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8,8a-octahydro-5,8-methano-2,3-naphthalene dicarboxylic anhydride, 1,2,3,4,5,6,7,7octachloro-3,6-methano-1,2,3,6-tetrahydrophthalic anhydride and mixturesthereof,

() an alkylene oxide selected from the group consisting of alkyleneoxides having from 2 to 12 carbon atoms, halogenated alkylene oxideshaving from 2 to 4 carbon atoms and from 1 to 3 halogen atoms andmixtures thereof,

the mole ratio of (a) to (b) being from 1:0.1 to 1:6 and the amount of(c) employed being such to reduce the acid number of the polyol to oneor less.

2. The polyol of claim 1 wherein the amine is ethylene diamine.

3. The polyol of claim 1 wherein the amine is toluene diamine.

4. The polyol of claim 1 wherein the amine is polymeric methylenedianiline.

5. The polyol of claim 1 wherein the anhydride is tetrabromophthalicanhydride.

6. The polyol of claim 1 wherein (c) is propylene e sle- 7. The polyolof claim 1 wherein the mole ratio of (a) to (b) is from 1:0.1 to 1:1.

8. A process for the preparation of an ester-containing amine-basedliquid polyol which comprises reacting at a temperature of from C. to C.for 0.5 hour to 10 hours.

(a) a condensate of an amine having at least two active hydrogen atomsselected from the group consisting of aliphatic amines having from oneto twenty carbon atoms and aromatic amines having from six to twelvecarbon atoms with an alkylene oxide selected from the group consistingof alkylene oxides having from 2 to 12 carbon atoms, halogenatedalkylene oxides having from 2 to 4 carbon atoms and from 1 to 3 halogenatoms and mixtures thereof,

(b) a halogen-containing organic acid anhydride selected from the groupconsisting of dichloromaleic anhydride, tetrabrornophthalic anhydride,tetrchlorophthalic anhydride,l,4,5,6,7,7-hexachlorobicyclo(2.2.1)-5-heptene-2,3-dicarboxylicanhydride, hereinafter called chlorendic anhydride, 1,4,5,6,7,7-hexachloro 2 methylbicyclo(2.2.1)-5-heptene-2,3- dicarboxylic anhydride,1,4,5,6,7,7 hexachlorobicyclo(2.2.1)-5-heptene-2-acetic 2 carboxylicanhydride, 5,6,7,8,9,9hexachloro-l,2,3,4,4a,5,'8,8a-octahydro-5,8-methano-2,3-naphthalenedicarboxylic anhydride, l,2,3,4,5,6,7,7-octachloro-3,6-methano 1,2,3,6-tetrahydrophthalic anhydride and mixtures thereof,

(c) an alkylene oxide selected from the group consisting of alkyleneoxides having from 2 to 12 carbon atoms, halogenated alkylene oxideshaving from 2 to 4 carbon atoms and from 1 to 3 halogen atoms andmixtures thereof,

in a mole ratio of (a) to (b) being from 1:01 to 1:6 and the amount of(c) employed being such to reduce the acid number of the polyol to oneor less.

References Cited UNITED STATES PATENTS 3,625,988 12/1971 Cyba 260468ROBERT GERSTL, Primary Examiner US. Cl. X.R.

gee-g5 v, 2.5 AQ, 268 PL, 4625 G, 475 r, 435 q

